CN1256361C - Preparation method of polypara dioxo cyclohexanone capable of raising molecular weight and conversion rate simultaneously - Google Patents
Preparation method of polypara dioxo cyclohexanone capable of raising molecular weight and conversion rate simultaneously Download PDFInfo
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- CN1256361C CN1256361C CN 200410040299 CN200410040299A CN1256361C CN 1256361 C CN1256361 C CN 1256361C CN 200410040299 CN200410040299 CN 200410040299 CN 200410040299 A CN200410040299 A CN 200410040299A CN 1256361 C CN1256361 C CN 1256361C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 title abstract description 18
- SUEVWEWAIVZWCQ-UHFFFAOYSA-N cyclohexane-1,2,3-trione Chemical compound O=C1CCCC(=O)C1=O SUEVWEWAIVZWCQ-UHFFFAOYSA-N 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 claims description 57
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 30
- 241000790917 Dioxys <bee> Species 0.000 claims description 29
- 230000009466 transformation Effects 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- 229960004217 benzyl alcohol Drugs 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- YJBMMHPCGWCCOH-UHFFFAOYSA-N octan-3-yl dihydrogen phosphate Chemical compound CCCCCC(CC)OP(O)(O)=O YJBMMHPCGWCCOH-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 11
- -1 rare earth salt Chemical class 0.000 abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000035800 maturation Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000012264 purified product Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003483 aging Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical class [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 2
- 229940050168 zinc lactate Drugs 0.000 description 2
- 235000000193 zinc lactate Nutrition 0.000 description 2
- 239000011576 zinc lactate Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- SSQIOAPXYBWOKP-UHFFFAOYSA-N [Nd].C(C)C(=O)C(=O)C Chemical compound [Nd].C(C)C(=O)C(=O)C SSQIOAPXYBWOKP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Polymerization Catalysts (AREA)
Abstract
The present invention discloses a preparation method of poly-P-dioxycyclohexanone capable of simultaneously enhancing molecular weight and conversion rates. The method comprises: p-dioxycyclohexanone and a catalyst are compounded according to a molar ratio of (800 to 10000) to 1, and under the conditions of no water, no oxygen and inert gas protection, the mixture is heated to 40 to 160 DEG C for polymerization, which obtains reaction products; after the obtained reaction products are purified and dried, purified products are obtained. The present invention is characterized in that the catalyst is a mutual-compounded catalytic system of aluminium alkyl or the rare earth salt of isopropyl alcohol; polymerization time is from 3 to 10 hours. The technological method has the advantages of maturation, simplicity, easy control and short production periodicity, which can be used for obtaining poly-P-dioxycyclohexanone whose molecular weight is from 70000 to 810000, and at the same time, monomer conversion can reach more than 84.5%.
Description
One, technical field
The invention belongs to the PPDO preparing technical field, be specifically related to a kind of preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously.
Two, background technology
PPDO is as a kind of novel material, be the earliest by U.S. Ethicon in the seventies later development come out.Because contain unique ehter bond in the PPDO molecular chain, the kindliness of molecular chain is good, it has been acquired widely use.Wherein the high-molecular weight PPDO just can be widely used in surgical sutures, screw, fixedly fasten, the framework material of orthopaedics immobilization material, tissue renovation material and medicament slow release system such as pin, anchor, hoop, mosquito forceps, hemostasis cream, suture clips, medicinal screen cloth, adhesive of medical.
Though from the seventies so far, people adopt stannous octoate (SnOct successively
2), zinc ethyl (ZnEt
2), triethyl aluminum (AlEt
3), aluminum isopropylate (Al (O
iPr)
3), zinc lactate (ZnLac
2), catalyzer such as lipase Lipase CA have successfully been realized the ring-opening polymerization to the dioxy pimelinketone, but make a general survey of these technology, be not difficult to find that selected these catalyzer are not that catalytic activity is low, polymerization velocity is slow, is exactly that monomeric transformation efficiency is low, the molecular weight of polymerisate is low, perhaps haves both at the same time.As people (US Patent 4 such as Doddi in 1977,052,988) adopt zinc ethyl catalysis to the ring-opening polymerization of dioxy pimelinketone, under comparatively harsh polymerizing condition, polymerization time reaches 72 hours, the intrinsic viscosity of the polymerisate that obtains is also only for 0.70dL/g, and zinc ethyl has pyrophoricity, makes its storage and use very inconvenient.People (US Patent 5 such as Forschener in 1997,652,331, WO 97,21753) adopt stannous octoate to make catalyzer, adopt dodecanol to realize ring-opening polymerization simultaneously to the dioxy pimelinketone as initiator, the ratio of monomer and catalyzer is 10000: 1, the highest weight that obtains polymerisate can reach 81,000, but its transformation efficiency only is 67%.People such as Kricheldorf in 1998 (Macromol.Chem.Phys.1998,199,1089-1097) adopted synthetic and stored all zinc lactate catalyzer very easily, also realized ring-opening polymerization to the dioxy pimelinketone.But under 100 ℃ of conditions, when M/C is 2000/1, reacted 14 hours, viscosity can only reach 0.95dL/g, and monomer conversion also has only 62%.2000, the Nishida of Japan, (Macromolecules 2000,33,6982-6986.) wait the people under the condition that does not have aided initiating to exist, adopt stannous octoate catalyst to realize equally to the ring-opening polymerization of dioxy pimelinketone, though under 100 ℃ of conditions, when M/C is 4900/1, reacted 20 hours, the molecular weight of polymkeric substance has reached 14.2 ten thousand, but monomer conversion has only 79.4%.In the same year, people such as Nishida (Jounal of Polymer Science Part A:Polym.Chem.2000,38,1560-1567) adopt the lipase Lipase CA of 5wt% as ring-opening polymerization catalyst, and under 60 ℃ of conditions, synthesized the nontoxic PPDO that does not contain any metal through 15h, its highest weight Mw only is 41,000.Raquez (Macromol.Rapid Commun.2000 in 2000,21,1063-1071.) etc. the people adopt aluminum isopropylate to make catalyzer also to have realized ring-opening polymerization to the dioxy pimelinketone, result of study shows, the intrinsic viscosity of PPDO [η] increases with the rising of the ratio M/I of monomer and aluminum isopropylate, have good controllability, but the highest intrinsic viscosity of institute's synthetic PPDO product only is 0.77dL/g, monomer conversion has only 70%.
Three, summary of the invention
The objective of the invention is defective, a kind of preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously is provided at the prior art existence.
The preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously provided by the invention, be will be to dioxy pimelinketone and catalyzer, be 800～10000: 1 proportioning in molar ratio, under the protection of anhydrous and oxygen-free and rare gas element, be heated to 40～160 ℃ of polymerizations and promptly get reaction product, it is characterized in that catalyzer is aluminum alkyls interworking catalyst system or Virahol rare earth salt; Polymerization time 3-10 hour.
Molecular weight with the PPDO of method provided by the invention preparation can reach 70000～810000, can reach more than 84.5% the monomeric transformation efficiency of dioxy pimelinketone.
The first component aluminum alkyls of the aluminum alkyls interworking catalyst system of selecting for use in aforesaid method is a triethyl aluminum, any in triisobutyl aluminium, the aluminium diethyl monochloride; Second component is phosphoric acid or is in lanthanum, neodymium, zinc, iron, cobalt, the nickel any with the cationic moiety, anionicsite is the cycloalkanes acidic group, the compound of any composition in Acetyl Acetone base, 2-ethylhexyl phosphoric acid ketone group, the 2-ethylhexyl phosphoric acid monoesters base; The 3rd component is any in water, methyl alcohol, ethanol, neopentyl alcohol, the phenylcarbinol.During interworking, can also select first component and the second component interworking, or first component and the 3rd component interworking.The method of interworking is known technology.As when aluminum alkyls interworking catalyst system is three component interworkings, at first in the catalyzer pipe arrangement, add second component, and with dry toluene with second components dissolved, inject the aluminum alkyls of first component then, 20～60 ℃ of following ageings more than 2 hours, cooling back slowly drips the 3rd component, wait that the gas that is produced stops after, it is standby slowly to return to room temperature.When being first component and the second component interworking when aluminum alkyls interworking catalyst system, at first in the catalyzer pipe arrangement, add second component, and with dry toluene with second components dissolved, inject the aluminum alkyls of first component then, 20～60 ℃ of following ageings more than 2 hours, it is standby slowly to return to room temperature.When being first component and the 3rd component interworking when aluminum alkyls interworking catalyst system, at first in the catalyzer pipe arrangement, add first component, slowly drip the 3rd component then, wait that the gas that is produced stops after, it is standby slowly to return to room temperature.Catalyst concn is in the first component aluminum alkyls, generally with 4 * 10
-7～3 * 10
-6Mole/microlitre is advisable, and wherein the mol ratio of first component and second component is 1～10: the mol ratio of 1, the three component and first component is 0.1-1: 1.
Rare earth element in the Virahol rare earth salt catalyst of selecting for use in aforesaid method is any among Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu.The preparation method of Virahol rare earth salt catalyst also is a known technology, being about to rare earth oxide joins in the excessive aqueous acetic acid, under reflux temperature, react to solution and be the water white transparency shape, stopped reaction, the unreacted excessive acetic acid and the aqueous solution are removed in distillation, obtain acetate rare-earth salts powder 40 ℃ of vacuum-dryings; 1: 1 in molar ratio ratio adds acetate rare-earth salts and metal Na then, and logical high pure nitrogen three times also keeps logical high pure nitrogen state, adds toluene from constant pressure funnel, reflux; After treating that Na is molten fully, add excessive Virahol again, reacted about one hour, be cooled to room temperature: under argon shield, filter a small amount of unreacted acetate rare-earth salts then, keep subnatant, promptly obtain the toluene solution of Virahol rare earth salt catalyst.
Because the present invention has adopted aluminum alkyls interworking catalyst system or Virahol rare earth salt to make catalyzer, so in aforesaid method, the water content of monomer to the dioxy pimelinketone required and can reduce greatly, all can be controlled at below the 200ppm, and polymerization temperature is preferably 80～100 ℃.
Preparation method provided by the invention has the following advantages:
1, uses preparation method provided by the invention, can not only obtain the high-molecular weight PPDO, use needs to satisfy, and can also improve monomer conversion greatly, obtain better economic benefit.
2, because the present invention just on the basis of preparation PPDO ordinary method, has adopted new catalyzer, thereby processing method maturation not only, simply, be easy to control, and for can prepare high molecular simultaneously, high monomer transformation efficiency PPDO has been opened up a new way.
3, because catalyst activity height of the present invention can obtain high molecular within a short period of time simultaneously, the PPDO of high monomer transformation efficiency, thereby shortened the production cycle greatly.
4,, thereby can under the prerequisite of the PPDO that obtains the same molecular amount, reduce greatly making excessive demands to dioxy pimelinketone monomer water content because the present invention has adopted aluminum alkyls interworking catalyst system or Virahol rare earth salt to make catalyzer.
5, the resulting high molecular PPDO of the present invention has not only still kept its excellent biological compatibility, Bioabsorbable and biological degradability, but also has kept its snappiness preferably.
Four, embodiment
Provide embodiment below so that the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field to some nonessential improvement and adjustment that the present invention has done, still belongs to protection scope of the present invention according to the invention described above content.
Embodiment 1
Present embodiment is to use AlEt
3-Nb (AcAc)
3-H
2O Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, Preparation of catalysts: also vacuumize adding methyl ethyl diketone neodymium (Nb (AcAc) in the catalyst preparation pipe that leads to nitrogen repeatedly in high bake
3) and dry toluene, inject triethyl aluminum (AlEt then
3) and under nitrogen protection, in 60 ℃ of ageings 2 hours, under agitation slowly drip the mixing solutions (H of water and 1,4 dioxane (DXO) after the cooling
2O/DXO=1/9), after question response stopped, it was standby to reduce to room temperature.AlEt
3With Nb (AcAc)
3Mol ratio be 8: 1, H
2O and AlEt
3Mol ratio be 0.5: 1.
2, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 120ppm dioxy pimelinketone 3.6 is restrained, and adds the AlEt that has prepared then while stirring
3-Nb (AcAc)
3-H
2O catalyzer 15.7 microlitres stir polymerization and promptly got reaction product in 10 hours in 80 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 8000: 1.
3, aftertreatment: polymerization is opened polymerization bottle after finishing, and PPDO is carried out extracting and purifying with solvent toluene handled 48 hours, and under 50 ℃, vacuum-drying to constant weight promptly gets 3.43 gram purifying things then, and monomer conversion is 95.3%.
With the PPDO that obtains, with phenol/1,1,2, (2: 3/w: w) mixing solutions is made solvent to the 2-tetrachloroethane, in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity [η] that records PPDO is 3.0dL/g, by Mark-Houwink equation [η]=K M with dark type viscometer
v α(α=0.63, K=79 * 10
-3Cm
3g
-1) molecular weight of the PPDO calculated is 480,000.
Embodiment 2
Present embodiment is to use AlEt
3-H
3PO
4-H
2O Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, the Preparation of catalysts method is not stated so omit because of identical with embodiment 1.That different is the proportioning of each component of present embodiment catalyzer: AlEt
3With H
3PO
4Mol ratio be 8: 1, H
2O and AlEt
3Mol ratio be 0.5: 1.
2, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 73ppm dioxy pimelinketone 3.6 is restrained, and adds the AlEt that has prepared then while stirring
3-H
3PO
4-H
2O catalyzer 15.7 microlitres stir polyase 13 and hour promptly get reaction product in 100 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 10000: 1,
3, aftertreatment: method is with embodiment 1, slightly.Gained purifying thing is 3.46 grams, and monomer conversion is 96.1%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 4.2dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 810,000.
Embodiment 3
Present embodiment is to use AlEt
3-H
2O Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, Preparation of catalysts: also vacuumize repeatedly in the catalyst preparation pipe of logical nitrogen in high bake, add triethyl aluminum (AlEt
3), and under agitation slowly drip the mixing solutions (H of water and 1,4 dioxane (DXO)
2O/DXO=1/9), wait that the gas that is produced stops after, it is standby to reduce to room temperature.H
2O and AlEt
3Mol ratio be 0.1: 1.
2, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 85ppm dioxy pimelinketone 3.6 is restrained, and adds the AlEt that has prepared then while stirring
3-H
2O catalyzer 31.4 microlitres stir polymerization and promptly got reaction product in 6 hours in 60 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 5000: 1.
3, aftertreatment: method is with embodiment 1, slightly.Gained purifying thing is 3.28 grams, and monomer conversion is 91%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 2.8dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 430,000.
Embodiment 4
Present embodiment is to use AlEt
3-La (AcAc)
3-CH
3OH Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, the Preparation of catalysts method is not stated so omit because of identical with embodiment 1.That different is the proportioning of each component of present embodiment catalyzer: AlEt
3With La (AcAc)
3Mol ratio be 10: 1, CH
3OH and AlEt
3Mol ratio be 0.3: 1.
3, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 132ppm dioxy pimelinketone 3.6 is restrained, and adds the AlEt that has prepared then while stirring
3-La (AcAc)
3-CH
3OH catalyzer 78.5 microlitres stir polymerization and promptly got reaction product in 8 hours in 120 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 2000: 1.
3, aftertreatment: method is with embodiment 1, slightly.Gained purifying thing is 3.04 grams, and monomer conversion is 84.5%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 2.1dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 270,000.
Embodiment 5
Present embodiment is with Al (i-Bu)
3-Zn (AcAc)
3-C
6H
5OH Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, the Preparation of catalysts method is not stated so omit because of identical with embodiment 1.That different is the proportioning of each component of present embodiment catalyzer: Al (i-Bu)
3With Zn (AcAc)
3Mol ratio be 1: 1, C
6H
5OH and Al (i-Bu)
3Mol ratio be 0.7: 1.
3, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 176ppm dioxy pimelinketone 3.6 is restrained, and adds the Al (i-Bu) that has prepared then while stirring
3-Zn (AcAc)
3-C
6H
50.78 milliliter of OH catalyzer stirs polymerization and promptly got reaction product in 5 hours in 40 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 1000: 1.
3, aftertreatment: method is with embodiment 1, slightly.Gained purifying thing is 3.04 grams, and monomer conversion is 84.5%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 1.4dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 140,000.
Embodiment 6
Present embodiment is to use AlEt
3-Nb (P
2O
4)
3-H
2O Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, the Preparation of catalysts method is not stated so omit because of identical with embodiment 1.That different is the proportioning of each component of present embodiment catalyzer: AlEt
3With Nb (P
2O
4)
3Mol ratio be 6: 1, H
2O and AlEt
3Mol ratio be 0.7: 1.
2, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 80ppm dioxy pimelinketone 3.6 is restrained, and adds the AlEt that has prepared then while stirring
3-Nb (P
2O
4)
3-H
2O catalyzer 31.4 microlitres stir polymerization and promptly got reaction product in 10 hours in 90 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 5000: 1,
3, aftertreatment: method is with embodiment 1, slightly.Gained purifying thing 3.29 grams, monomer conversion is 91.5%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 2.5dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 360,000.
Embodiment 7
Present embodiment is with three lanthanum isopropoxides (La (O
iPr)
3) the Preparation of Catalyst PPDO.All operations all are at anhydrous and oxygen-free, carry out under the protection of high-purity argon gas.
1, Preparation of catalysts: also vacuumize repeatedly in the catalyst preparation pipe of logical nitrogen in high bake, with 0.8 gram La
2O
3Add in the excessive aqueous acetic acid, under reflux temperature, react to solution and be the water white transparency shape, stopped reaction, the unreacted excessive acetic acid and the aqueous solution are removed in distillation, and 40 ℃ of vacuum-dryings obtain white La (OCOCH
3)
3Powder.Added La (OCOCH in 1: 1 in molar ratio
3)
3, metal Na, logical high pure nitrogen three times also keeps logical high pure nitrogen state, adds 10 milliliters of toluene from constant pressure funnel, reflux, treat that Na is molten fully after, add 1 milliliter of i-C again
3H
7OH reacted one hour, was cooled to room temperature, removed by filter NaOCOCH then under the high-purity argon gas protection
3With a small amount of unreacted La (OCOCH
3)
3, keep subnatant, be resulting three lanthanum isopropoxides (La (O
iPr)
3The catalyzer toluene solution.
2, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 95ppm dioxy pimelinketone 3.6 is restrained, and adds the La (O that has prepared then while stirring
iPr)
30.2 milliliter of catalyzer stirs polymerization and promptly got reaction product in 4 hours in 160 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 800: 1.
3, aftertreatment: polymerization is opened polymerization bottle after finishing, and PPDO is carried out extracting and purifying with solvent toluene handled 48 hours, and under 50 ℃, vacuum-drying to constant weight promptly gets 3.15 gram purifying things then, and monomer conversion is 87.5%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 0.9dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 70,000.
Embodiment 8
Present embodiment is with three Virahol neodymium (Nb (O
iPr)
3) Preparation of Catalyst is poly-to the dioxy cyclohexanone.All operations all are at anhydrous and oxygen-free, carry out under the protection of high pure nitrogen.
1, Preparation of catalysts: also vacuumize repeatedly in the catalyst preparation pipe of logical nitrogen in high bake, with 0.8 gram Nb
2O
3Add in the excessive aqueous acetic acid, under reflux temperature, react to solution and be the water white transparency shape, stopped reaction, the unreacted excessive acetic acid and the aqueous solution are removed in distillation, and 40 ℃ of vacuum-dryings obtain white Nb (OCOCH
3)
3Powder.Added Nb (OCOCH in 1: 1 in molar ratio
3)
3, metal Na, logical high pure nitrogen three times also keeps logical high pure nitrogen state, adds 10 milliliters of toluene from constant pressure funnel, reflux, treat that Na is molten fully after, add 1 milliliter of i-C again
3H
7OH reacted one hour, was cooled to room temperature, removed by filter NaOCOCH then under the high-purity argon gas protection
3With a small amount of unreacted Nb (OCOCH
3)
3, keep subnatant.Be resulting three Virahol neodymium (Nb (O
iPr)
3The catalyzer toluene solution.
2, polymerization: also vacuumizing repeatedly in the polymerization bottle of logical nitrogen through high bake, adding purity more than 99.5%, water content is 110ppm dioxy pimelinketone 3.6 is restrained, and adds the Nb (O that has prepared then while stirring
iPr)
3Catalyzer 80 microlitres stir polymerization and promptly got reaction product in 10 hours in 100 ℃ constant temperature oil bath behind the tube sealing.Mol ratio to dioxy pimelinketone and catalyzer is 2000: 1.
3, aftertreatment: polymerization is opened polymerization bottle after finishing, and PPDO is carried out extracting and purifying with solvent toluene handled 48 hours, and under 50 ℃, vacuum-drying to constant weight promptly gets 3.26 gram purifying things then, and monomer conversion is 90.5%.
With the PPDO that obtains, with the testing method that embodiment 1 provides, the intrinsic viscosity [η] that records PPDO is 1.5dL/g, and the molecular weight of the PPDO of the Equation for Calculating that provides by embodiment 1 is 150,000.
Claims (5)
1, a kind of preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously, this method is with to dioxy pimelinketone and catalyzer, be 800～10000: 1 proportioning in molar ratio, under the protection of anhydrous and oxygen-free and rare gas element, be heated to 40～160 ℃ of polymerizations and promptly get reaction product, it is characterized in that catalyzer is an aluminum alkyls interworking catalyst system, the first component aluminum alkyls of this system is a triethyl aluminum, any in triisobutyl aluminium, the aluminium diethyl monochloride; Second component is phosphoric acid or is in lanthanum, neodymium, zinc, iron, cobalt, the nickel any with the cationic moiety that anionicsite is any compound formed in cycloalkanes acidic group, Acetyl Acetone base, ethylhexyl dihydrogen phosphate base, the 2-ethylhexyl phosphoric acid monoesters base; The 3rd component is any in water, methyl alcohol, ethanol, neopentyl alcohol, the phenylcarbinol, during interworking, can also select first component and the second component interworking, or first component and the 3rd component interworking; Polymerization time 3-10 hour.
2, the preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously according to claim 1, it is characterized in that the mol ratio of first component and second component is 1～10 in the catalyzer: the mol ratio of 1, the three component and first component is 0.1-1: 1.
3, the preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously according to claim 1 and 2 is characterized in that should being controlled at below the 200ppm the water content of dioxy pimelinketone.
4, the preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously according to claim 1 and 2 is characterized in that polymerization temperature is 80～100 ℃.
5, the preparation method that can improve the PPDO of molecular weight and transformation efficiency simultaneously according to claim 3 is characterized in that polymerization temperature is 80～100 ℃.
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